DE1139639B - Process for the production of heat-resistant molded parts or moving with a tack-free surface - Google Patents

Description

INTERNAT. KL. C 08 g

GERMAN

PATENT OFFICE

I15119IVd / 39b

REGISTRATION DATE: JULY 17, 1958

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL: NOVEMBER 15, 1962

The invention relates to a method of manufacture of heat-resistant molded parts or coatings with a tack-free surface by hardening mold or Coating compositions - at normal or higher temperature - containing unsaturated alkoxy groups Silanes, oxygen-containing catalysts, accelerators, Drying agents, polymerizable monomeric vinyl and / or allyl compounds and optionally linear unsaturated polyesters and / or unsaturated, low molecular weight, branched ones Poly mixed esters - which can also contain halogen - and contain fillers, which are characterized by this is that one cures molding or coating compounds containing as unsaturated alkoxy groups Silanes three- or polyunsaturated alkoxysilanes, the double bonds of which are in the alkoxy groups, contain.

It is known to halosilanes, with glycols underneath Elimination of hydrogen halide to form hydroxyalkoxysilanes implement and these products a mixture of linear unsaturated polyesters and to add polymerizable vinyl monomers in a small amount in order to adhere to the polyester resins To improve fiberglass products in the manufacture of laminates.

It is also known to add unsaturated alkoxysilanes with maleic or fumaric acid or their esters to polymerize of peroxides, to hydrolyze the polymer and the polysiloxane compounds formed to add oil alkyd resins in solvents in order to obtain heat-resistant stoving enamels.

It is also known to hydrolyze silanes in ethereal solution with mineral acids to give polysiloxanes and to add alkyd resins to the solution obtained, which are also used as stoving enamels. Polysiloxanes produced in other ways were also condensed into unsaturated polyesters, however this does not result in products with a tack-free surface.

It is also known to use vinylalkoxysilanes with acids or bases in an aqueous medium for pretreatment of fiberglass in the manufacture of polyester fiberglass laminates.

The use of unsaturated organic silicon compounds, for example dimethoxymethyl vinylsilane, as monomers mixed with linear unsaturated polyester resins is already known. However, moldings made from such products have no tack-free surfaces, which can be attributed to this is that the organic silicon compounds used have only one unsaturated group included per Si atom.

Method of manufacture

of heat-resistant molded parts

or moving with a tack-free surface

Applicant:

Chemical works in Witten

Limited liability company, Witten, Arthur-Imhausen-Str. 92 a

Dipl.-Chem. Edith Behnke, née Dembski,

Hamburg-Harburg,

and Dr. rer. nat. Helmut Wulff, Witten, have been named as the inventor

The silanes containing unsaturated alkoxy groups used according to the invention, their preparation not claimed here .wird are made from suitable halosilanes and unsaturated halosilanes using known processes produced monohydric alcohols with elimination of hydrogen halide.

As halosilanes, for. B. vinyl trichlorosilane, Methyl trichlorosilane, ethyl trichlorosilane, silicon tetrachloride and dimeric halosilanes are suitable. As unsaturated monohydric alcohols, for. B. allyl alcohol, Endomethylene tetrahydrobenzyl alcohol, /? - Hydroxyethyl allyl ether can be used.

As polymerizable monomeric vinyl and / or allyl compounds, for. B. styrene, vinyl toluene, n-vinyl butyl ether, acrylic and methacrylic acid esters, diallyl adipate, triallyl cyanurate and saturated allyl esters and unsaturated acids can be used.

The usual linear unsaturated polyesters result with the tri- or polyunsaturated alkoxysilanes generally cloudy mixtures and inhomogeneous polymers. You can therefore only with the simultaneous presence of low molecular weight, unsaturated, spatially branched mixed polyesters and suitable vinyl and / or allyl compounds polymerized with the unsaturated alkoxysilanes to form homogeneous products. However, are halogen-containing, linear unsaturated polyesters z. B.

209 707/348

Contain tetrachlorophthalic acid residues, compatible with the alkoxysilanes. These can easily be cured to give clear, homogeneous copolymers. Instead of the halogen-containing linear unsaturated polyesters, it is likewise possible to use mixtures of halogen-containing, linear unsaturated polyesters and halogen-free linear unsaturated polyesters, optionally in a mixture with the polyesters to be used according to the invention. ■ half a few hours at 100 ° C, optionally under pressure of 5 kg / cm ² in molds to form water-white, very heat-resistant, hard and extremely scratch-resistant, solvent-resistant, infusible moldings, sheets or the like. Polymerized. The surfaces are completely tack-free when exposed to atmospheric oxygen.

The self-polymerization of vinyl-tri- (allyloxy) -silane is extremely slow. In the case of

As low molecular weight, unsaturated, spatial degradation of peroxide catalysts and temperatures

from 100 to 120 ° C only a small amount of polymerisation can be observed after 24 hours.

Example 2

40 parts of commercially available monomeric n-butyl methacrylate are stirred into 60 parts of vinyl tri- (allyloxy) silane. The water-white, thin-bodied mixture is mixed with 2 parts of commercially available 50% tert-butyl perbenzoate added and applied at 120 ° C

Branched polyesters are for copolymerization with those containing three or more unsaturated alkoxy groups Suitable silanes are those which are composed of 1 mol of polyhydric, saturated or unsaturated alcohol, the number of moles of saturated and / or unsaturated dicarboxylic acids corresponding to the functionality of the alcohol and the corresponding number of moles of saturated and / or unsaturated monohydric alcohols exist.

The individual half an hour to be used for the production of the 20 according to the invention at a pressure of 10 kg / cm ² cured in molds within a molding and coatings. There are obtained thermally constituent, such as unsaturated alkoxy groups-containing, stable, light-colored molded articles which are infusible in the tendon silanes, monomeric polymerizable vinyl, as opposed to those produced using polymeth and / or allyl compounds, halogen-containing unsaturated acrylates and in saturated linear polyesters, unsaturated linear polyesters, aggressive solvents and monomeric n-butyl and mixed esters, can only be slightly swollen alone or in a mixture of methacrylate. Will use. the polymerization with 5 to 10 parts of styrene oxide as

The curing of the three or more unsaturated polymerization is carried out, so the silanes and / or vinyl containing alkoxy groups proceed more slowly and more evenly, and it can be applied to and / or allyl compounds and / or unsaturated 30 this way even without applying pressure in the case of linear polyesters and low molecular weight, unsaturated temperatures of 80 to 100 ° C castings obtained th, spatially branched polyesters or at
Place of unsaturated linear polyesters and low molecular weight, unsaturated, spatially branched ones
Polyesters, halogen-containing, linear polyesters, 35
optionally mixed with linear halogen-free ones
unsaturated polyesters, and / or low molecular weight
unsaturated, spatially branched mixed polyesters
for the production of moldings and coatings

is ^{mixed 1} with the help of conventional polymerization catalysts, 40 and poured into molds. Within some such as B. diacyl peroxides, peracid esters and hy- hours polymerized the mixture with Temperadroperoxden, but also, for example, with aralkylene oxides carried out.

The curing of the molding compounds can take place with or without application, depending on the choice of components of pressure and at low temperatures, preferably at temperatures of 20 to 30 ° C, or at elevated temperatures, preferably at temperatures of 80 to 150 ° C, are carried out. Will

worked under pressure, pressures of 1 to 50 ether are produced and stabilized with 0.01% hydroquinone -30 kg / cm ² . is lized, with 30 parts of vinyl-tri- (allyloxy-

ethoxy) silane, made from vinyl trichlorosilane and ß-hydroxyethyl allyl ether, mixed and with 2 parts commercial 50% tert-butyl perbenzoate and 0.8 parts of a commercial cobalt octoate solution, which contains 1% active cobalt, added. The liquid mixture is applied as a coating on a suitable Underground, such as B. metal or ceramic, painted and at 120 to 130 ° C for about 1 hour burned in. The coating hardens to a tack-free, scratch-resistant, bright, transparent, solvent-free, which have non-sticky surfaces even when exposed to air.

Example 3

In 50 parts of vinyl-tri- (allyloxy) -silane there are 50 parts commercially available monomeric vinyl n-butyl ether is stirred in and the water-white liquid mixture with 2 parts of commercially available benzoyl peroxide paste

doors from 80 to 100 ° C to hard, bright, heat-resistant Moldings with a tack-free surface.

Example 4

70 parts of a mixed poly ester with an acid number of 25, which in a known manner from 1 mol of pentaerythritol, 3MoI Maleic anhydride, Va moles of phthalic anhydride, moles of adipic acid and 4.1 moles of diglycol monoethyl

The use of accelerators and drying agents is also possible. Even in thin ones Layers are always tack-free when exposed to air Surfaces available.

The molded parts to be produced according to the invention can optionally contain color pigments and fillers as well as fibrous carrier materials.

The process is illustrated by the following examples, parts being parts by weight.

example 1

In 50 parts of vinyl-tri- (allyloxy) -silane, prepared by a known process from vinyl-trichlorosilane and allyl alcohol, 50 parts of commercially available triallyl cyanurate are stirred in and the resulting water-white liquid mixture with the addition of 2 parts of commercially available 50% benzoyl peroxide paste with internal stability Layer.

Example 5

50 parts of the unsaturated poly ester described in Example 4, 15 parts of a poly mixed ester with the acid number 15, which is stabilized with 0.02 vol of hydroquinone, which is composed of 1 mol of pentaerythritol, 4 mol

Adipic acid and 4.4 moles of allyl alcohol, 18 parts of a linear, unsaturated polyester with the acid number 28, which is stabilized with 0.01% hydroquinone and in a known manner from 2 mol Maleic anhydride, 1 mole of phthalic anhydride and 3.3 moles of 1,2-propylene glycol, 7 parts Commercially available vinyl toluene and 10 parts of methyl tri- (allyloxy) silane are with 2 parts of commercially available 5O% tert-butyl perbenzoate and 0.8 parts of a Commercially available cobalt octoate solution containing 1% cobalt is added and 100 parts of titanium dioxide are added rubbed into a colored varnish. The paint is painted on metal parts and applied within 1 hour Baked in at 120 ° C. The result is a heat-resistant, tack-free, hard, scratch-resistant layer with good Shine.

Claims (1)

PATENT CLAIM: Process for the production of heat-resistant molded parts or coatings with a tack-free surface by curing molding or coating compounds - at normal or higher temperatures - silanes containing unsaturated alkoxy groups, oxygen-containing catalysts, accelerators, drying agents, polymerizable monomeric vinyl and / or allyl compounds and optionally linear ones unsaturated polyesters and / or unsaturated, low molecular weight, branched polyesters - which can also be halogen-like - and contain fillers, characterized in that molding or coating compounds are cured, the silanes containing as unsaturated alkoxy groups are tri- or polyunsaturated alkoxysilanes, their double bonds in the Alkoxy groups are included. Considered publications:
Belgian Patent No. 546 203;
French patent specification No. 1152149. © 209 707/348 11.62